JPS6115149B2 - - Google Patents
Info
- Publication number
- JPS6115149B2 JPS6115149B2 JP53068222A JP6822278A JPS6115149B2 JP S6115149 B2 JPS6115149 B2 JP S6115149B2 JP 53068222 A JP53068222 A JP 53068222A JP 6822278 A JP6822278 A JP 6822278A JP S6115149 B2 JPS6115149 B2 JP S6115149B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum oxide
- carbide alloy
- alloy body
- sintered carbide
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 75
- 239000010410 layer Substances 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 31
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 229910052735 hafnium Inorganic materials 0.000 claims description 17
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- -1 hafnium ions Chemical class 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 150000001247 metal acetylides Chemical class 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 27
- 238000000151 deposition Methods 0.000 description 19
- 230000008021 deposition Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/148—Composition of the cutting inserts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
Landscapes
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Chemically Coating (AREA)
- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】
本発明は薄い極度に耐摩耗性の表面層で被覆さ
れた焼結炭化物合金体に関する。本発明はまたか
かる被覆体を作る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sintered carbide alloy body coated with a thin, extremely wear-resistant surface layer. The invention also relates to a method of making such a coating.
例えばチツプ形成機のための植刃の如き圧縮
し、半融させた焼結炭化物合金体の耐摩耗性は、
硬質表面層を付与することによつてかなり増大せ
しめうることは知られている。特に金属炭化物、
金属窒化物または金属酸化物が、焼結炭化物合金
芯または基体上に薄い層（例えば１〜20μｍの厚
さを有する層）として付与されている。またある
場合には、お互いにその上に付与した二つまたは
数個の異なる層からなる薄い被覆を用いることに
よつて更に利点を得ることができることも知られ
ている。特に外側セラミツク層の下に中間層とし
て炭化物または窒化物を使用することを挙げるこ
とができる。酸化アルミニウム（Al2O3）および
酸化ジルコニウム（ZrO2）はかかるセラミツク表
面層の例である。表面被覆を付与する一つの主要
な方法はCDV法即ち化学的蒸着法である、この
方法においてはガス状成分間の反応によつて熱基
体上に被覆が沈着する。酸化アルミニウム被覆製
造のため使用されている最も普通の化学的蒸着法
は、直接蒸発させるかあるいはアルミニウム金属
と塩素または塩化水素との間の反応によつて形成
される塩化アルミニウムの水素還元と、直接蒸発
させるか、あるいは水素と二酸化炭素によつて形
成された蒸気、または酸素との反応を含む方法で
ある。 For example, the wear resistance of a compressed and semi-melted sintered carbide alloy body, such as a cutting blade for a chip forming machine, is
It is known that this can be increased considerably by applying a hard surface layer. Especially metal carbides,
The metal nitride or metal oxide is applied as a thin layer (for example a layer having a thickness of 1 to 20 μm) on a sintered carbide alloy core or substrate. It is also known that in some cases further advantages can be obtained by using thin coatings consisting of two or several different layers applied on top of each other. Mention may be made, in particular, of using carbides or nitrides as an intermediate layer below the outer ceramic layer. Aluminum oxide (Al 2 O 3 ) and zirconium oxide (ZrO 2 ) are examples of such ceramic surface layers. One major method of applying surface coatings is the CDV or chemical vapor deposition process, in which the coating is deposited onto a hot substrate by reaction between gaseous components. The most common chemical vapor deposition methods used for the production of aluminum oxide coatings are hydrogen reduction of aluminum chloride, which is formed by direct evaporation or reaction between aluminum metal and chlorine or hydrogen chloride; The process involves vaporizing or reacting hydrogen with the vapor formed by carbon dioxide or oxygen.
所望される耐摩耗性を有する酸化アルミニウム
の好適な硬く、多結晶質の緊密な良く接着した被
覆は、通常約950℃以上の付着温度で得られるに
すぎない。より低い温度では、酸化アルミニウム
のガンマおよび／またはシータ相からなるゆるい
粉末状の付着が通常得られる。約1000℃以上の付
着温度で、切削工具に好適であると通常認められ
ている酸化アルミニウム相はα相である。しかし
ながらこの酸化アルミニウムの相は、1000℃以下
の付着温度では化学的蒸着によつて純粋な状態で
作ることを通常期待できない高温相である。1000
℃以下の温度で付着するα酸化アルミニウムの安
定性は、被覆される基体またはガス相から来る不
純物またはドープ剤の存在によつて決る。純粋な
α酸化アルミニウム基体を用いるとき、化学的蒸
着によつてα酸化アルミニウムの配向重複成長が
約1500℃以上の付着温度で生ずるのみである。 Suitable hard, polycrystalline, tight, well-adhered coatings of aluminum oxide with the desired abrasion resistance are usually only obtained at deposition temperatures of about 950° C. or higher. At lower temperatures, loose powder-like deposits consisting of gamma and/or theta phases of aluminum oxide are usually obtained. At deposition temperatures of about 1000° C. or higher, the aluminum oxide phase generally accepted as suitable for cutting tools is the alpha phase. However, this aluminum oxide phase is a high temperature phase that cannot normally be expected to be produced in pure form by chemical vapor deposition at deposition temperatures below 1000°C. 1000
The stability of alpha aluminum oxide deposited at temperatures below 0 C depends on the presence of impurities or dopants coming from the substrate being coated or from the gas phase. When using pure alpha aluminum oxide substrates, oriented overgrowth of alpha aluminum oxide by chemical vapor deposition only occurs at deposition temperatures above about 1500 DEG C.
このことから、被覆工具の製造に当つて通常使
用される温度で、多相酸化アルミニウム被覆を得
る危険がかなりあることが明らかである。多相被
覆においては、各相の境界域がかなり機械的に弱
い帯域を構成し、従つてそれらは早期工具破損の
原因となりうる。 It is clear from this that there is a considerable risk of obtaining a multiphase aluminum oxide coating at the temperatures normally used in the production of coated tools. In multiphase coatings, the boundary areas of each phase constitute zones of considerable mechanical weakness and therefore they can be a source of premature tool failure.
酸化アルミニウム被覆の付着は、基体および／
またはガス相から種々な種の拡散を含む。被覆の
形成を支配する各拡散の相互作用、核形成および
成長機構は非常に微妙なもので、不均質付着の形
成を容易に生ぜしめることができる。かかる機構
はしばしば制御困難であるから、安定な特別な酸
化アルミニウム相を提供しうる方法が、単一相酸
化アルミニウム被覆を有する焼結炭化物体が、多
相酸化アルミニウム被覆と比較したときすぐれた
より一貫した性能を有することが期待しうること
から最も有利であると考えられる。 The deposition of the aluminum oxide coating is applied to the substrate and/or
or involving the diffusion of various species from the gas phase. The diffusion interactions, nucleation and growth mechanisms governing coating formation are very subtle and can easily give rise to the formation of heterogeneous deposits. Since such mechanisms are often difficult to control, methods that can provide a stable special aluminum oxide phase may result in sintered carbide bodies with single-phase aluminum oxide coatings being superior and more consistent when compared to multi-phase aluminum oxide coatings. It is considered to be the most advantageous because it can be expected to have a high performance.
本発明によればチツプ形成機に関して非常に重
大な相からなる酸化アルミニウム被覆を設けた焼
結炭化物合金体を作ることができることを見出し
た。本質的に単相である酸化アルミニウムはカツ
パ相からなり、その製造は一定の良く制御された
工程および指針によつて形成された。層は被覆さ
れた焼結炭化物合金体のみならず非被覆基体上に
付与でき、また多くの種々な種類の多層被覆中の
表面層または中間層としても使用できる。被覆は
耐摩耗性炭化物、窒化物、炭化窒化物および／ま
たは硼化物の中間層上に付与するのが好ましい。
特にこれらの炭化物、炭化窒化物、窒化物および
硼化物は、元素Ti、Zr、Hf、Ｖ、Nb、Ta、Cr、
Mo、Ｗ、SiおよびＢ（元素Ｂで形成される硼化
物を除く）の一つで形成させる。中間層としてチ
タンの炭化物、窒化物および／または炭化窒化物
が特に好適である。 It has now been found that according to the invention it is possible to produce a sintered carbide alloy body provided with an aluminum oxide coating, which is a very important phase for chip forming machines. Aluminum oxide, which is essentially single-phase, consists of a Katsupah phase, and its manufacture has been shaped by certain well-controlled processes and guidelines. The layer can be applied not only to a coated cemented carbide alloy body, but also to an uncoated substrate, and can be used as a surface layer or intermediate layer in many different types of multilayer coatings. Preferably, the coating is applied on an intermediate layer of wear-resistant carbides, nitrides, carbonitrides and/or borides.
In particular, these carbides, carbonitrides, nitrides and borides contain the elements Ti, Zr, Hf, V, Nb, Ta, Cr,
It is formed from one of Mo, W, Si, and B (excluding borides formed by element B). Titanium carbides, nitrides and/or carbonitrides are particularly suitable as intermediate layers.
本発明による焼結炭化物合金体の製造または被
覆の製造は、付着工程中、本質的に四価のチタン
および／またはジルコニウムおよび／またはハフ
ニウムイオンの特定の制御された量で酸化アルミ
ニウム被覆をドーピングすることによつて行なう
ことができ、かくすると、独占的にまたは殆ど独
占的にカツパアルミナが形成される。 The production of the sintered carbide alloy body or the production of the coating according to the invention involves doping the aluminum oxide coating with specific and controlled amounts of essentially tetravalent titanium and/or zirconium and/or hafnium ions during the deposition process. This can be done by a method such that exclusively or almost exclusively katsupa alumina is formed.
チタンおよび／またはジルコニウムおよび／ま
たはハフニウムは、酸化アルミニウムの付着に使
用する通常のガス混合物中に、ハロゲン化チタ
ン、ジルコニウムまたはハフニウム、特に四塩化
チタンを加えることによつて、酸化アルミニウム
被覆に混入することができる。酸化アルミニウム
および酸化チタンの共付着のため上述したガス混
合物にハロゲン化チタンを加えることは、複合ア
ルフア酸化アルミニウム／セスキ酸化チタン
（Ti2O3）被覆を作るため従来より使用されてい
た。しかしながら本発明は沈着ガス混合物に加え
るべきハロゲン化物の量を正確に決定し、かくし
て従来の酸化アルミニウム被覆の品質と比較した
とき殆ど独占的に、全く予期せざる程独占的にカ
ツパアルミナの形成をもたらすような方法で、チ
タンおよび／またはジルコニウムおよび／または
ハフニウムイオンを酸化アルミニウムに混入でき
るようにしたことに関する。チタンおよび／また
はジルコニウムおよび／またはハフニウムが反応
器中に正しい濃度および原子価状態（＋４）の下
で存在するとき、その一部または全部が被覆中に
入り、カツパ相を形成させるのであろう（この説
明は理論的には複雑であり、未だ明確にはなつて
いない、しかし先の説明において、既知の方法は
チタンが多分３価イオンとして加えられ、通常の
α酸化アルミナの形成をもたらすということがで
きる）。 Titanium and/or zirconium and/or hafnium are incorporated into the aluminum oxide coating by adding titanium, zirconium or hafnium halides, especially titanium tetrachloride, to the usual gas mixtures used for depositing the aluminum oxide. be able to. The addition of titanium halides to the gas mixtures described above for co-deposition of aluminum oxide and titanium oxide has traditionally been used to create composite alpha aluminum oxide/sesquititanium oxide (Ti 2 O 3 ) coatings. However, the present invention precisely determines the amount of halide to be added to the deposition gas mixture, thus resulting in the formation of Katupa alumina almost exclusively and quite unexpectedly exclusively when compared to the quality of conventional aluminum oxide coatings. The present invention relates to a method in which titanium and/or zirconium and/or hafnium ions can be mixed into aluminum oxide. When titanium and/or zirconium and/or hafnium is present in the reactor under the correct concentration and valence state (+4), some or all of it will enter the coating and form the Katupa phase ( This explanation is theoretically complex and not yet clear, but in the previous explanation, the known method is that the titanium is probably added as a trivalent ion, resulting in the formation of the usual alpha alumina oxide. ).
本発明にとつて重要なことは、基体または中間
層の表面の酸化状態を決定する酸化アルミニウム
付着法の開始条件にもある。例えば炭化チタンの
中間層の場合に、酸化アルミニウム付着法開始前
の酸化条件は酸化アルミニウムのカツパ相を与え
なくて、その代りに酸化アルミニウムのアルフア
相を与える。 Also of importance to the invention are the starting conditions of the aluminum oxide deposition process, which determine the oxidation state of the surface of the substrate or intermediate layer. For example, in the case of a titanium carbide interlayer, the oxidation conditions prior to starting the aluminum oxide deposition process do not provide a cuppa phase of aluminum oxide, but instead give an alpha phase of aluminum oxide.
酸化アルミニウムで被覆する前の中間炭化チタ
ン層の予備酸化は既に文献に提示されている。か
くして得られる酸化チタンは多かれ少なかれ下の
炭化チタン層によつて溶解されて、オキシ炭化物
を形成するか、あるいは酸化アルミニウム層によ
つて溶解されて混合酸化物を形成することができ
る。炭化チタン層中へ酸素移行がある場合、炭化
チタンのかなりの範囲の非理論量と、酸化チタン
と炭化チタンの相互溶解度のため、オキシ炭化物
が形成する。 Preoxidation of intermediate titanium carbide layers before coating with aluminum oxide has already been proposed in the literature. The titanium oxide thus obtained can be dissolved to a greater or lesser extent by the underlying titanium carbide layer to form an oxycarbide, or by the aluminum oxide layer to form a mixed oxide. When there is oxygen migration into the titanium carbide layer, oxycarbide is formed due to the considerable non-stoichiometric content of titanium carbide and the mutual solubility of titanium oxide and titanium carbide.
最も驚いたことには、カツパ酸化アルミニウム
の被覆がアルフア相のものよりもすぐれているこ
とを見出したことにある、何故ならばアルフア変
態はカツパ相よりも密であるからである（カツパ
相3.25Kg/dm3に対して3.99Kg/dm3である）。ここ
でできる説明は、これはカツパ相の観察された微
細な粒子の大きさによるか、あるいはカツパ酸化
アルミニウム層と基体例えば炭化チタン層の間に
生ずる改良された結合によるのであるということ
である。改良された結合はカツパ酸化アルミニウ
ムが本発明によつて得られたとき、炭化チタン層
の頂部帯域上または中に過剰の酸化アルミニウム
が存在しないという理由によるものと考えられ
る。酸化チタンの形成は下にある炭化チタンに対
して容積膨張を含む、これは炭化チタンの表面帯
域での接着に有害な効果を有しうる。 Most surprisingly, we found that the coating of Katsupa aluminum oxide is superior to that of the alpha phase, since the alpha transformation is denser than the Katsupa phase (Katsupa phase 3.25 Kg/dm 3 vs. 3.99Kg/dm 3 ). Possible explanations here are that this is due to the observed fine grain size of the Katsupa phase or to the improved bond that occurs between the Katsupa aluminum oxide layer and the substrate, such as a titanium carbide layer. The improved bonding is believed to be due to the fact that when Kappa aluminum oxide is obtained according to the invention, there is no excess aluminum oxide on or in the top zone of the titanium carbide layer. The formation of titanium oxide involves a volumetric expansion relative to the underlying titanium carbide, which can have a detrimental effect on adhesion at the surface zone of the titanium carbide.
市場で入手でき、二重に被覆された（酸化アル
ミニウム−炭化チタン）、焼結炭化物合金品質に
おいて、かなりの量のカツパ酸化アルミニウムも
形成される、事実表面の２〜98％はカツパ酸化ア
ルミニウムからなり、残余はアルフア酸化アルミ
ニウムからなる。この場合、カツパ酸化アルミニ
ウムの量の分散はかなり著しいものである。更に
アルフア酸化アルミニウムの円形部域の大きさは
実に大きく10〜200μｍである。表面の大きな部
分がアルフア相からなると円形スポツトがしばし
ば合体し、カツパ酸化アルミニウムの不規則な形
の部域を残す。アルフア酸化アルミニウムの重積
した部域は望ましくない、何故ならばそれらは容
易に破壊し、それらが工具刃の重要な帯域に位置
を占めるようになつたとき、チツプまたは加工片
によつて運び去れることになるからである。 In the dual coated (aluminum oxide-titanium carbide), sintered carbide alloy qualities available on the market, significant amounts of Katsupa aluminum oxide are also formed, in fact between 2 and 98% of the surface is from Katsupa aluminum oxide. The remainder consists of alpha aluminum oxide. In this case, the dispersion of the amount of katsupa aluminum oxide is quite significant. Furthermore, the size of the circular area of alpha aluminum oxide is quite large, ranging from 10 to 200 μm. When a large portion of the surface consists of alpha phase, the circular spots often coalesce, leaving irregularly shaped areas of Katupa aluminum oxide. Stacked areas of alpha aluminum oxide are undesirable because they break easily and are carried away by chips or workpieces when they occupy a critical zone of the tool edge. This is because it will result in a loss.
本発明によれば、アルフア酸化アルミニウムの
量を一致した方法で15％以下、好ましくは10％以
下に減少させることができ、また残存アルフア相
スポツトの大きさを約10μｍ以下、好ましくは６
μｍ以下に減少させることができることをここに
見出した。 According to the invention, the amount of alpha aluminum oxide can be reduced in a consistent manner to less than 15%, preferably less than 10%, and the size of the residual alpha phase spots can be reduced to less than about 10 μm, preferably 6 μm.
It has now been discovered that it can be reduced to below μm.
アルフア相スポツトの大きさおよび量および面
積の間の関係を第１図に示す。従来より知られて
いる酸化アルミニウム被覆においては、前述した
如く、相対的に大きなアルフア相スポツト、およ
びアルフア相スポツトの大きさに関する大きな変
動のみならずアルフア相の量の大きな変動を見出
すことができる。この面積の下限を図の曲線Ｄ−
Ｅによつてしるす。本発明によれば、アルフア相
スポツトの大きさおよび発生率をそれらが第１図
の面積AOB内、好ましくは面積A′OB′内に入る
ように規制すると性質を大きく改良できることを
ここに見出した。 The relationship between the size, amount and area of alpha phase spots is shown in FIG. In the previously known aluminum oxide coatings, as mentioned above, relatively large alpha-phase spots and large variations in the size of the alpha-phase spots as well as large variations in the amount of alpha-phase can be found. The lower limit of this area is the curve D-
Marked by E. According to the present invention, it has now been discovered that the properties can be greatly improved by controlling the size and incidence of alpha phase spots so that they fall within the area AOB, preferably within the area A'OB' of FIG. .
更に本発明の別の利点は、劇的に短縮した製造
時間をもたらす増大された付着速度にある。加え
るハロゲン化物の量によつて、二つ以上のフアク
ターによつてハロゲン化物ドープ剤なしで得られ
る成長速度以上の成長速度が得られる。被覆の製
造速度における増大とは別に、成長速度の増大
は、被覆が高温にさらされる時間を短縮する、そ
の結果として高温に曝露されることによる被覆組
織における望ましからぬ変化の生ずる可能性が著
しく減少することで、被覆の品質に直接的な利益
をもたらす。 Yet another advantage of the present invention resides in increased deposition rates resulting in dramatically reduced manufacturing times. Depending on the amount of halide added, two or more factors provide growth rates that are greater than those obtained without the halide dopant. Apart from an increase in the manufacturing rate of the coating, an increase in the growth rate reduces the time that the coating is exposed to high temperatures, with the result that undesirable changes in the coating structure may occur due to exposure to high temperatures. The significant reduction has a direct benefit on the quality of the coating.
酸化アルミニウム層は任意の通常の方法で付着
させることができる、しかしチタンおよび／また
はジルコニウムおよび／またはハフニウムドープ
剤を加えて、化学蒸着によつて付着させるのが好
ましい。これは焼結炭化物基体を中間層で被覆し
たとき、あるいは実際の酸化アルミニウム層付与
前または後に連続的に幾つかの層を付与または形
成させるときにも適用できる。カツパ酸化アルミ
ニウム被覆の化学蒸着は中間層（または他の可能
な表面層）の付着とは別に作ることができる、し
かし同じ装置で連続的に作るのが好ましい、かく
すると中間層の表面の酸化を制御して行なうこと
ができる。表面の過度の酸化は避けるべきであ
る、何故ならば例えば炭化チタンの酸化は容積膨
張および組織の変化をもたらし、接着の消失をも
たらすからである。 The aluminum oxide layer can be deposited by any conventional method, but is preferably deposited by chemical vapor deposition with the addition of titanium and/or zirconium and/or hafnium dopants. This is also applicable when coating the cemented carbide substrate with an intermediate layer or when applying or forming several layers in succession before or after the actual application of the aluminum oxide layer. The chemical vapor deposition of the Katsupa aluminum oxide coating can be made separately from the deposition of the interlayer (or other possible surface layer), but is preferably made sequentially in the same equipment, thus preventing surface oxidation of the interlayer. It can be done under control. Excessive oxidation of the surface should be avoided, since oxidation of, for example, titanium carbide leads to volume expansion and textural changes, leading to loss of adhesion.
酸化アルミニウム層の厚さは通常0.1〜20μｍ
でしばしば0.2〜10μｍであるが、特に0.3〜３μ
ｍである。しかしながら付与する酸化物層は0.5
〜２μｍの厚さが好ましい。アルミナ被覆の上の
みならず下にある中間層または連続付与した層の
厚さは、通常同じ大きさ、即ち0.1〜20μｍであ
る。耐摩耗性の炭化物、窒化物、炭化窒化物およ
び／または硼化物の中間層を使用する場合には、
厚さは通常１〜８μｍであり、1.5〜７μｍが好
ましい。 The thickness of the aluminum oxide layer is usually 0.1-20μm
often between 0.2 and 10 μm, but especially between 0.3 and 3 μm.
It is m. However, the applied oxide layer is 0.5
A thickness of ~2 μm is preferred. The thickness of the intermediate layer or successively applied layer above as well as below the alumina coating is usually of the same size, ie from 0.1 to 20 μm. When using a wear-resistant carbide, nitride, carbonitride and/or boride intermediate layer,
The thickness is usually 1 to 8 μm, preferably 1.5 to 7 μm.
カツパ酸化アルミニウム被覆を付着させるた
め、ハロゲン化アルミニウム好ましくは塩化アル
ミニウム（AlCl3）の水素還元および水蒸気または
酸素との反応を含む方法を使用できる。ハロゲン
化アルミニウムは、固体または液体の形のものを
蒸発させることによつて、またはアルミニウム金
属を塩素または塩化水素と反応させることによつ
てガスの形で作ることができる。水蒸気は蒸発に
よつてガスの形で作るとよい、あるいは水素と二
酸化炭素との反応によつて作るのが好ましい。酸
化アルミニウムをドーピングするため四塩化チタ
ンは液体の蒸発によつて蒸気の形で作る。チタ
ン、ジルコニウムまたはハフニウムの他のハロゲ
ン化物を使用するとき、蒸気は同じ方法で作るこ
とができる。各反応成分を、被覆されるべき焼結
炭化物合金試料を置いた反応室中に通す。試料は
誘電加熱によつて直接加熱してもよく、あるいは
例えば電気抵抗加熱で支持プレートまたは反応器
を加熱することによる間接的加熱でもよい。付着
温度は700〜1200℃の範囲であるが、950℃〜1150
℃が好ましい、実際の温度は存在する不純物また
は使用するドーピング剤の種類によつて決る。 To deposit the Katsupa aluminum oxide coating, a method involving hydrogen reduction of an aluminum halide, preferably aluminum chloride (AlCl 3 ) and reaction with water vapor or oxygen can be used. Aluminum halides can be made in gaseous form by evaporating solid or liquid forms or by reacting aluminum metal with chlorine or hydrogen chloride. Water vapor may be produced in gaseous form by evaporation, or preferably by reaction of hydrogen and carbon dioxide. For doping aluminum oxide, titanium tetrachloride is produced in vapor form by evaporation of a liquid. When using other halides of titanium, zirconium or hafnium, steam can be made in the same way. Each reactant is passed into a reaction chamber containing the sintered carbide alloy sample to be coated. The sample may be heated directly by dielectric heating or indirectly, for example by heating the support plate or reactor with electrical resistance heating. The deposition temperature ranges from 700 to 1200℃, but from 950℃ to 1150℃
C. is preferred; the actual temperature will depend on the impurities present or the type of doping agent used.
反応成分ガス混合物中の塩化アルミニウムおよ
び水蒸気（または二酸化炭素または酸素）濃度は
好ましくはほぼ理論量であるべきである。化学的
蒸着の場合、四価ハロゲン化物の濃度は、反応器
に供給するガスの全量の0.03〜0.5％、好ましく
は0.2％以下にすべきである。付着を化学的蒸着
方法以外の方法によつて行なうときには、相当す
るハロゲン化物の量を使用すべきである。また
CO2およびH2の濃度は注意して制御することが重
要である。推奨される四価ハロゲン化物の量は二
酸化炭素と塩化アルミニウムのほぼ理論量の割合
にする。反応器中がより還元性の状態にある場
合、二酸化炭素対水素または水蒸気対水素のより
低い比は、より大量の四価ハロゲン化物を加える
ことを必要とする。ガス相の全圧は１〜760トル
の範囲であることができるが、30〜80トルが好ま
しい。付着が上述した条件に従つて注意深く制御
されないときには、アルフアまたはその他の望ま
しからぬ酸化アルミニウム相がかなりの量で形成
される。 The aluminum chloride and water vapor (or carbon dioxide or oxygen) concentrations in the reactant gas mixture should preferably be approximately stoichiometric. In the case of chemical vapor deposition, the concentration of tetravalent halides should be between 0.03 and 0.5% of the total amount of gas fed to the reactor, preferably below 0.2%. Corresponding amounts of halide should be used when deposition is carried out by methods other than chemical vapor deposition. Also
It is important that the concentrations of CO2 and H2 are carefully controlled. The recommended amount of tetravalent halide is approximately the stoichiometric ratio of carbon dioxide and aluminum chloride. If there are more reducing conditions in the reactor, a lower ratio of carbon dioxide to hydrogen or steam to hydrogen requires the addition of a larger amount of tetravalent halide. The total pressure of the gas phase can range from 1 to 760 Torr, but is preferably from 30 to 80 Torr. If deposition is not carefully controlled according to the conditions described above, significant amounts of alpha or other undesirable aluminum oxide phases are formed.
チタンおよび／またはジルコニウムおよび／ま
たはハフニウムドーピング剤の添加は酸化アルミ
ニウムの付着速度をかなり増大させる。得られた
結果の例として、第２図に、添加した四塩化チタ
ンの量（容量％）の関数として成長速度を示すグ
ラフを示す。この図から例えば約0.05％の四塩化
チタンの添加が成長速度の３倍の増大を与えたこ
と（0.1μm/hrから約0.3μm/hrへ）を計画でき
る。 The addition of titanium and/or zirconium and/or hafnium dopants considerably increases the rate of aluminum oxide deposition. As an example of the results obtained, FIG. 2 shows a graph showing the growth rate as a function of the amount (% by volume) of titanium tetrachloride added. From this figure it can be calculated that, for example, the addition of about 0.05% titanium tetrachloride gave a three-fold increase in the growth rate (from 0.1 μm/hr to about 0.3 μm/hr).
カツパ酸化アルミニウムの被覆は通常酸化物層
中に例えばそれぞれチタン、ハフニウムまたはジ
ルコニウムの二酸化物の形でチタン、ハフニウム
および／またはジルコニウムのある量を含有す
る。Ti、Hfおよび／またはZrの添加は酸化アル
ミニウム被覆形成中酸化物の形成に影響を与え
る。二酸化チタンが層の一部である場合、量は通
常0.5〜10％である。 Katsupa aluminum oxide coatings usually contain a certain amount of titanium, hafnium and/or zirconium in the oxide layer, for example in the form of titanium, hafnium or zirconium dioxide, respectively. The addition of Ti, Hf and/or Zr affects the formation of oxides during aluminum oxide coating formation. If titanium dioxide is part of the layer, the amount is usually 0.5-10%.
以下の実施例は本発明による表面被覆焼結炭化
物体を作るため使用した種々な条件およびかかる
焼結炭化物体を試験して得られた結果を示す。 The following examples illustrate various conditions used to make surface coated sintered carbonized bodies according to the present invention and the results obtained when such sintered carbonized bodies were tested.
実施例 １
ISOグレードM20の多数の焼結炭化物合金切削
植刃を、６μｍの厚さの炭化チタン層で被覆し、
次いて続いて１μｍの厚さのカツパ酸化アルミニ
ウム層で被覆した。Example 1 A number of sintered carbide alloy cutting inserts of ISO grade M20 were coated with a 6 μm thick titanium carbide layer,
It was then subsequently coated with a 1 μm thick layer of Kappa aluminum oxide.
カツパ酸化アルミニウム付着条件は次のとおり
であつた。 The conditions for adhering aluminum oxide to Katsupa were as follows.
反応成分ガス混合物 H2 90 ％
AlCl3 ２ ％
CO2 ６ ％
TiCl4 0.1％
CO 1.9％
ガス流速 ２ m/s
ガス混合物の圧力 50 トル（6.7kpa）
温 度 1010 ℃（1283〓）
付着時間 1.5時間
カツパ酸化アルミニウム被覆は完全に密で、多
結晶質で良く接着していた。Reactant gas mixture H 2 90% AlCl 3 2% CO 2 6% TiCl 4 0.1% CO 1.9% Gas flow rate 2 m/s Pressure of gas mixture 50 torr (6.7 kpa) Temperature 1010 °C (1283〓) Deposition time 1.5 Time The Katupa aluminum oxide coating was completely dense, polycrystalline and well bonded.
本発明により被覆した植刃の性能の試験におい
て、四価ハロゲン化物の添加を含まない従来より
使用されていた方法に従つて被覆した植刃の寿命
と比較したとき20％までの植刃の寿命の増大が得
られた。 In tests of the performance of blades coated according to the present invention, the lifetime of blades coated according to the present invention was up to 20% when compared to the life of blades coated according to conventionally used methods that do not include the addition of tetravalent halides. was obtained.
実施例 ２
被覆を３μｍの炭化チタンの中間層および３μ
ｍの酸化アルミニウムの外層で構成したこと以外
は実施例１と同様にして多数の焼結炭化物合金切
削植刃を被覆した。酸化アルミニウムの付着時間
を５時間に増大した、一方炭化物付着のための時
間は半分にした、付着条件は実施例１と同じであ
る。Example 2 Coating with a 3μm titanium carbide intermediate layer and a 3μm titanium carbide intermediate layer.
A large number of sintered carbide alloy cutting inserts were coated in the same manner as in Example 1, except that the outer layer was made of aluminum oxide. The deposition conditions are the same as in Example 1, with the aluminum oxide deposition time increased to 5 hours, while the time for carbide deposition was halved.
外側被覆は99％までカツパ相酸化アルミニウム
からなり、残余が直径５μｍを越えない丸い区域
の形でのアルフア酸化アルミニウムであつた。 The outer coating consisted of up to 99% of Katsupa phase aluminum oxide, the remainder being alpha aluminum oxide in the form of rounded areas not exceeding 5 μm in diameter.
実施例１の方法と同じ方法でこれらの被覆の性
能の比較試験において、100％という大きい植刃
の寿命の増大が見出された。 In a comparative test of the performance of these coatings in the same manner as in Example 1, a 100% increase in large blade life was found.
実施例 ３
ISOグレードM20の多数の焼結炭化物合金植刃
を、焼結炭化物の基体上に直接カツパ酸化アルミ
ニウムで被覆した。酸化物被覆のため実施例１と
同じ条件を使用した。この場合にも、従来の方法
で酸化アルミニウムで被覆した植刃に比して約20
％まで植刃の寿命の増大が得られた。試験は約１
％の炭素含有率を有する鋼の丸削として行なつ
た。Example 3 A number of ISO grade M20 sintered carbide alloy inserts were coated with Katsupa aluminum oxide directly onto a sintered carbide substrate. The same conditions as in Example 1 were used for the oxide coating. In this case as well, compared to implanted blades coated with aluminum oxide using the conventional method, approximately 20%
An increase in the lifespan of the grafted blade by up to % was obtained. The test is about 1
It was carried out as round cutting of steel with a carbon content of %.
実施例 ４
焼結炭化物合金体を２μｍの窒化ハフニウムの
中間層および１μｍのカツパ酸化アルミニウムの
表面層で被覆した。二つの層CVD法で付与し
た。中間層は通常の方法で付与したが、表面層は
下記条件で付与した。Example 4 A sintered carbide alloy body was coated with a 2 μm intermediate layer of hafnium nitride and a 1 μm surface layer of Katsupa aluminum oxide. It was applied using a two-layer CVD method. The intermediate layer was applied by a conventional method, but the surface layer was applied under the following conditions.
反応成分ガス混合物 H2 89 ％
AlCl3 ２ ％
CO2 ７ ％
ZrCl4 0.05％
CO 1.95％
ガス流速 2.5 m/s
ガス混合物の圧力 55 トル
温 度 1015 ℃
付着時間 １ 時間
結果として少なくとも90％カツパ相からなる良
く接着した酸化アルミニウム層が得られた。Reactant gas mixture H 2 89% AlCl 3 2% CO 2 7% ZrCl 4 0.05% CO 1.95% Gas flow rate 2.5 m/s Pressure of gas mixture 55 Torr temperature 1015 °C Deposition time 1 hour Resulting in at least 90% Katsupa phase A well-adhered aluminum oxide layer consisting of
第１図は化学的蒸着によつて炭化チタン被覆焼
結炭化物合金基体上に付着した酸化アルミニウム
被覆中のアルフア酸化アルミニウムスポツトの大
きさと面積被覆率の関係を示す図であり、第２図
は炭化チタン被覆焼結炭化物合金基体上への酸化
アルミニウムの化学的蒸着中の四塩化チタンの添
加効果を示すグラフである。
Figure 1 shows the relationship between the size and area coverage of alpha aluminum oxide spots in the aluminum oxide coating deposited on the titanium carbide-coated sintered carbide alloy substrate by chemical vapor deposition, and Figure 2 1 is a graph showing the effect of adding titanium tetrachloride during chemical vapor deposition of aluminum oxide onto a titanium-coated sintered carbide alloy substrate.
Claims (1)
も一つの薄い耐摩耗性表面層を付与した、結合剤
金属以外に少なくとも一種の炭化物を含有する焼
結炭化物合金体において、酸化アルミニウムの少
なくとも85％がカツパ相からなり、存在するとき
には主としてアルフア相を構成する残余が、大き
くても10μｍの大きさを有する表面部分またはス
ポツトとして形成され、表面部の大きさおよび発
生をそれらが第１図の区域AOB好ましくは区域
A′OB′内にあるように規制したことを特徴とする
焼結炭化物合金体。 ２ 酸化アルミニウム層の厚さが0.1〜20μｍで
ある特許請求の範囲第１項記載の焼結炭化物合金
体。 ３ 元素Ti、Zr、Hf、Ｖ、Nb、Ta、Cr、Mo、
Ｗ、Siおよび／またはＢで形成した、耐摩耗性の
炭化物、窒化物、炭化窒化物および／または硼化
物の薄い中間層を、酸化アルミニウム層および焼
結炭化物合金体の間に付与する特許請求の範囲第
１項または第２項記載の焼結炭化物合金体。 ４ 中間層の厚さが１〜８μｍである特許請求の
範囲第３項記載の焼結炭化物合金体。 ５ 中間層がチタンの炭化物、窒化物および／ま
たは炭化窒化物からなる特許請求の範囲第３項ま
たは第４項記載の焼結炭化物合金体。 ６ 酸化アルミニウム層がチタン、ジルコニウム
および／またはハフニウムの添加物を含有する特
許請求の範囲第１項〜第５項の何れか一つに記載
の焼結炭化物合金体。 ７ アルミニウムのハロゲン化物の１種以上を含
有するガスを高温で焼結体または基体上にもたら
し焼結炭化物合金体を製造する方法において、四
価チタン、ジルコニウムおよび／またはハフニウ
ムイオンのドーピング剤添加物をガス中に全供給
ガス量の0.03〜0.5％の量で加えることを特徴と
する酸化アルミニウムより本質的になる少なくと
も一つの薄い耐摩耗性表面層を付与した、結合剤
金属以外に少なくとも一種の炭化物を含有する焼
結炭化物合金体であつて、酸化アルミニウムの少
なくとも85％がカツパ相からなり、存在するとき
には主としてアルフア相を構成する残余が、大き
くても10μｍの大きさを有する表面部分またはス
ポツトとして形成され、表面部の大きさおよび発
生をそれらが第１図の区域AOB内にあるように
規制した焼結炭化物合金体の製造法。 ８ 酸化アルミニウム層の厚さが0.1〜20μｍで
ある特許請求の範囲第７項記載の焼結炭化物合金
体の製造法。 ９ 元素Ti、Zr、Hf、Ｖ、Nb、Ta、Cr、Mo、
Ｗ、Siおよび／またはＢで形成した、耐摩耗性の
炭化物、窒化物、炭化窒化物および／または硼化
物の薄い中間層を、酸化アルミニウム層および焼
結炭化物合金体の間に付与する特許請求の範囲第
７項または第８項記載の焼結炭化物合金体の製造
法。 １０ 中間層の厚さが１〜８μｍである特許請求
の範囲第９項記載の焼結炭化物合金体の製造法。 １１ 中間層がチタンの炭化物、窒化物および／
または炭化窒化物からなる特許請求の範囲第９項
または第１０項記載の焼結炭化物合金体の製造
法。 １２ 酸化アルミニウム層がチタン、ジルコニウ
ムおよび／またはハフニウムの添加物を含有する
特許請求の範囲第７項〜第１１項の何れか一つに
記載の焼結炭化物合金体の製造法。Claims: 1. A sintered carbide alloy body containing at least one carbide other than a binder metal, provided with at least one thin wear-resistant surface layer consisting essentially of aluminum oxide, 85% is composed of the Katsupa phase, and when present, the remainder, which mainly constitutes the alpha phase, is formed as a surface part or spot with a size of at most 10 μm, and the size and occurrence of the surface part are shown in Figure 1. area AOB preferably area
A sintered carbide alloy body characterized by being regulated to be within A′OB′. 2. The sintered carbide alloy body according to claim 1, wherein the aluminum oxide layer has a thickness of 0.1 to 20 μm. 3 elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
Claims providing a thin interlayer of wear-resistant carbides, nitrides, carbonitrides and/or borides formed of W, Si and/or B between the aluminum oxide layer and the sintered carbide alloy body The sintered carbide alloy body according to the range 1 or 2. 4. The sintered carbide alloy body according to claim 3, wherein the intermediate layer has a thickness of 1 to 8 μm. 5. The sintered carbide alloy body according to claim 3 or 4, wherein the intermediate layer is made of titanium carbide, nitride and/or carbonitride. 6. The sintered carbide alloy body according to any one of claims 1 to 5, wherein the aluminum oxide layer contains an additive of titanium, zirconium, and/or hafnium. 7. A method for producing a sintered carbide alloy body in which a gas containing one or more halides of aluminum is brought onto a sintered body or substrate at high temperature, in which a doping agent additive of tetravalent titanium, zirconium and/or hafnium ions is added. is added to the gas in an amount of 0.03 to 0.5% of the total gas supplied, at least one other than the binder metal, imparted with at least one thin wear-resistant surface layer consisting essentially of aluminum oxide. A sintered carbide alloy body containing carbides, in which at least 85% of the aluminum oxide consists of a katupah phase, and when present, the remainder, which mainly constitutes an alpha phase, has a surface portion or spot having a size of at most 10 μm. A method for manufacturing a sintered carbide alloy body in which the size and occurrence of the surface portions are controlled so that they are within the area AOB of FIG. 8. The method for producing a sintered carbide alloy body according to claim 7, wherein the aluminum oxide layer has a thickness of 0.1 to 20 μm. 9 Elements Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
Claims providing a thin interlayer of wear-resistant carbides, nitrides, carbonitrides and/or borides formed of W, Si and/or B between the aluminum oxide layer and the sintered carbide alloy body A method for producing a sintered carbide alloy body according to item 7 or 8. 10. The method for producing a sintered carbide alloy body according to claim 9, wherein the intermediate layer has a thickness of 1 to 8 μm. 11 The intermediate layer is titanium carbide, nitride and/or
or a method for producing a sintered carbide alloy body according to claim 9 or 10, which is made of carbonitride. 12. The method for producing a sintered carbide alloy body according to any one of claims 7 to 11, wherein the aluminum oxide layer contains an additive of titanium, zirconium, and/or hafnium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7706706A SE406090B (en) | 1977-06-09 | 1977-06-09 | COATED HARD METAL BODY AND WAY TO PRODUCE A SUITABLE BODY |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5410314A JPS5410314A (en) | 1979-01-25 |
| JPS6115149B2 true JPS6115149B2 (en) | 1986-04-22 |
Family
ID=20331555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6822278A Granted JPS5410314A (en) | 1977-06-09 | 1978-06-06 | Coated sintered carbide body and method of making same |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US4180400A (en) |
| JP (1) | JPS5410314A (en) |
| AT (1) | AT366721B (en) |
| BR (1) | BR7803700A (en) |
| CA (1) | CA1133524A (en) |
| CH (1) | CH640274A5 (en) |
| DE (1) | DE2825009C2 (en) |
| ES (1) | ES470609A1 (en) |
| FR (1) | FR2393852A1 (en) |
| GB (1) | GB2006727B (en) |
| IT (1) | IT1096522B (en) |
| MX (1) | MX149305A (en) |
| SE (1) | SE406090B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0436273Y2 (en) * | 1986-04-04 | 1992-08-27 |
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-
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- 1978-06-06 US US05/913,035 patent/US4180400A/en not_active Expired - Lifetime
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- 1978-06-07 MX MX173723A patent/MX149305A/en unknown
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- 1978-06-09 CH CH633478A patent/CH640274A5/en not_active IP Right Cessation
- 1978-06-09 AT AT0419778A patent/AT366721B/en not_active IP Right Cessation
-
1981
- 1981-12-16 US US06/331,314 patent/USRE31526E/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0436273Y2 (en) * | 1986-04-04 | 1992-08-27 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2393852B1 (en) | 1980-10-31 |
| AT366721B (en) | 1982-05-10 |
| CA1133524A (en) | 1982-10-12 |
| BR7803700A (en) | 1979-03-13 |
| US4180400A (en) | 1979-12-25 |
| GB2006727B (en) | 1982-04-15 |
| DE2825009C2 (en) | 1986-09-25 |
| SE7706706L (en) | 1978-12-10 |
| IT7824305A0 (en) | 1978-06-07 |
| MX149305A (en) | 1983-10-14 |
| DE2825009A1 (en) | 1978-12-14 |
| ES470609A1 (en) | 1979-10-01 |
| CH640274A5 (en) | 1983-12-30 |
| GB2006727A (en) | 1979-05-10 |
| SE406090B (en) | 1979-01-22 |
| USRE31526E (en) | 1984-02-28 |
| FR2393852A1 (en) | 1979-01-05 |
| IT1096522B (en) | 1985-08-26 |
| JPS5410314A (en) | 1979-01-25 |
| ATA419778A (en) | 1979-11-15 |
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